Melting and subsolidus reactions in the system K2O−CaO−MgO−Al2O3−SiO2−H2O: experiments and petrologic application

Experiments with synthetic starting materials of muscovite, phlogopite, zoisite, kyanite and quartz were performed in the pressure temperature range 10–25 kbar, 640–780° C under water excess conditions. The reaction muscovite+zoisite+quartz+vapor=liquid+kyanite was bracketed at 10.5 kbar/689–700° C, 15.5 kbar/709–731° C and 20 kbar/734–745° C. The equivalent reaction in the Mg-bearing system muscovite_ss +zoisite+quartz+vapor=liquid+kyanite+phlogopite_ss lies at the same temperature around 10 kbar and approximately 10° C higher around 20 kbar, compared with the Mg-free reaction. At slightly higher temperatures formation of melt and tremolite_ss was reversibly observed from the assemblage phlogopite_ss+zoisite +kyanite+quartz around 10.5 kbar/690–710° C, 15.5 kbar/720–750° C and 20.5 kbar/745–760° C. In the subsolidus region, the reaction muscovite_ss+talc_ss+ tremolite_ss=phlogopite_ss+zoisite+quartz+vapor were located in the range 700° C/16.7–19.0 kbar and 740° C/19.7–20.8 kbar. From these data, a wedge shaped stability field of phlogopite_ss+zoisite+quartz appears with a high P, T termination around 21 kbar/755° C. Muscovite+tremolite+talc or kyanite comes in at higher pressures. These phase relations are in qualitative accord with petrographic observations from high pressure metamorphic areas. Formation and crystallization of melts in rocks of a wide compositional range involving zoisite/epidote has been ascribed to relatively high pressures and is consistent with experimentally determined stability fields in the simplified KCMASH system.     

Stability relations of K2Mg5Si12O30, and end member of the merrihueite-roedderite group of meteoritic minerals

The phase K₂Mg₅Si₁₂O₃₀ was synthesized both hydrothermally and dry under a variety of pressures and temperatures, and its stability relations were determined. Under hydrothermal conditions it exhibits a lower stability limit lying at 595°C, 1 kb, and 650°C, 2 kb, due to its breakdown into the hydrous assemblage quartz+KMg_2.5Si₄O₁₀(OH)₂ (a mica phase). Its upper temperature stability under hydrothermal conditions is given by its incongruent melting to MgSiO₃+liquid. Near 820° C at a fluid pressure of approximately 6.5 kb the two univariant curves for these breakdown reactions intersect thus limiting the stability field to lower fluid pressures. — Under anhydrous conditions K₂Mg₅Si₁₂O₃₀ becomes unstable at pressures between approximately 7 and 32.5 kb due to its incongruent melting to the assemblage MgSiO₃+quartz (or coesite)+liquid; this melting curve has a pronounced negative slope. No subsolidus breakdown assemblage was encountered at 32.5 kb down to temperatures as low as 750°C. This behavior is probably due to the instability of other ternary compounds in the system K₂O-MgO-SiO₂ at high pressures and thus to the existence of very low-temperature eutectics involving only binary and unary solid phases plus liquid.It is likely that these stability relations provide a model for those of the natural minerals merrihueite and roedderite which contain Na and Fe₊₂ partly substituting for K and Mg and which were encountered in several meteorites. Therefore, the cosmic events leading to the formation of these minerals must have taken place at relatively low pressures and high temperatures, especially when water was present. The bulk compositions of these minerals appear to be incompatible with average chondritic matter under equilibrium conditions. Hence merrihueite and roedderite are not likely to be found in equilibrated chondrites which contain feldspars instead.     

Melting relations of basalt-andesile-rhyolite-H2O and a pelagic red clay at 30 kb

An olivine basalt, a tonalite (andesite), a granite (rhyolite), and a red clay (pelagic sediment) were reacted, with known quantities of water in sealed noble metal capsules, in a piston-cylinder apparatus at 30 kb pressure. For the pelagic sediment, with H₂O+=7.8% and no additional water, the liquidus temperature is 1240°C, the primary phases are garnet and kyanite. The subsolidus phase assemblage is phengite mica+garnet+clinopyroxene+coesite+kyanite. With 5 wt.% water added, the liquidus temperatures and primary phases for the calc-alkaline rocks are 1280°-1180°-1080°, garnet+clinopyroxene, garnet, and quartz respectively. Garnet and clinopyroxene occur throughout the melting interval of the olivine tholeiite for all water contents. Garnet is joined by clinopyroxene 80° below the andesite plus 5% H₂O liquidus, quartz is joined by clinopyroxene 180° below the rhyolite plus 5% H₂O liquidus. The subsolidus phase assemblage is garnet+clinopyroxene+coesite+minor kyanite for all the calc-alkaline compositions. We conclude that calc-alkaline andesites and rhyolites are not equilibrium partial melting pruducts of subducted oceanic crust consisting of olivine tholeiite basalt and siliceous sediments. Partial melting in subduction zones produces broadly acid and intermediate liquids, but these liquids lie off the calc-alkaline basalt-andesite-rhyolite join and must undergo modification at lower pressures to produce calcalkaline magmas erupted in overlying island arcs.     

Stability of pyrope-quartz in the system MgO-Al2O3-SiO2

Pyrope and quartz are stable with respect to aluminous enstatite and sillimanite at 1400 °C, 20 kb and at 1100 °C, 16 kb. The phase boundary limiting the coexistence of pyrope and quartz towards lower pressures is probably slightly curved. A slope of 15 bars/°C at 1400° and of 10 bars/°C at 1000 °C has been estimated from the experimental data. Between 1050 and 1100 °C the curve is intersected by the kyanite-sillimanite phase boundary. The calculated slope of the reaction aluminous enstatite + kyanite pyrope + quartz is negative (ca. 18–25 bars/°C). The existence of a negative slope has been demonstrated experimentally. Experimental evidence indicates that the assemblage aluminous enstatite and sillimanite is metastable with respect to sapphirine + quartz at high temperature. The invariant point involving the phases pyrope-sapphirine-aluminous enstatite-sillimanite-quartz is estimated to occur at 1125°±25 °C and 16±1 kb. A model phase diagram for the silicasaturated part of the system MgO-Al₂O₃-SiO₂ has been constructed. The position of three invariant points in this system has been estimated on the basis of presently available data.     

Enthalpy of formation of Fe3Al2Si3O12 (almandine) by high temperature alkali borate solution calorimetry

A high-temperature solution calorimetric method suitable for thermochemical studies of anhydrous minerals containing Fe²⁺ ions has been developed. The method is based on an oxide melt solvent with 52 wt% LiBO₂ and 48 wt% NaBO₂ maintained at a temperature of 750°C. In a first application of this method the enthalpies of solution of synthetic almandine, fayalite, a mixture of fayalite plus quartz on FeSiO₃ composition, and natural quartz were measured. For the reaction:

the enthalpy change at 1023 K is ?3.82 ± 0.87 kcal, based on fayalite, quartz, corundum and almandine, and ?5.96 ± 0.90 kcal based on the fayalite plus quartz mixture, corundum, and almandine. These values lead to standard molar enthalpies of formation of almandine from the oxides at 1023 K of ?14.10 ± 1.22 kcal and ?16.24 ± 1.74 kcal, respectively. The measured enthalpy of formation of almandine is less negative by several kilocalories than values derived from analysis of the phase equilibrium work of Hsu (1968), but in closer agreement with the phase equilibrium study of O'Neill and Wood (1979) and similar to the phase equilibrium deduction of Froese (1973).The agreement of the present almandine enthalpy of formation with O'Neill and Wood (1979) and Froese (1973) suggests that almandine entropies at 298 K to be obtained from their studies, in the range 79–81 cal/K, are more nearly correct than the several estimates based on oxide sum and volume-entropy systematics, most of which are much lower.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

Sudoite,di/trioctahedral chlorite: A stable low-temperature phase in the system MgO-Al2O3-SiO2-H2O

Sudoite, ideally (Mg₂Al₃)[AlSi₃O₁₀](OH)₈, was synthesized in small quantities from a number of starting materials using seeds of the natural mineral. Because its powder X-ray diffraction pattern is very similar to that of normal, trioctahedral chlorite, a technique based on relative intensities of 001-peaks of the chlorite-type phases was used, in addition to the standard X-ray method, to determine growth or breakdown of sudoite. Seeded runs indicate that sudoite is more stable than at least five alternative mineral assemblages in the system MgO-Al₂O₃-SiO-H₂O below about 370°–390° C at water pressures up to at least 7 kbar. At higher temperatures sudoite decomposes into assemblages of normal chlorite with an Al₂SiO₅-phase and either quartz or pyrophyllite. However, the exact locations of the univariant breakdown curves could not be determined due to very low reaction rates. Schreinemakers analyses indicate that the assemblage sudoite+quartz represents the low-temperature equivalent of the common pair chlorite+pyrophyllite, and that sudoite+quartz is limited to water pressures below about 7 kbar because of its reaction to form the high-pressure phase Mg-carpholite; however, in the absence of quartz, the stability fields of sudoite and of Mg-carpholite overlap at pressures above 7 kbar.These stability data are in general agreement with two well-documented sudoite occurrences in quartz veins cutting highly oxidized, low-pressure manganiferous metapelites, and with one occurrence in a silica-deficient high-pressure metamorphic metabauxite. Sudoites may be more common in low-grade metamorphic rocks than known thus far, but they may not be stable under surface conditions.     

The reaction enstatitess+sillimanite ⇌ sapphiriness+quartz in the system MgO-Al2O3-SiO2

The univariant pressure temperature curve of the reaction aluminous enstatite solid solution+sillimanitesapphirine solid solution+quartz was determined experimentally in the pressure range between 12 and 20 kb. It is defined by four reversals at 15 kb, 1140°+10°C; at 1190°C, 15.9±1 kb; at 1300°C, 17.2±1 kb; and at 1400°C, 18±1 kb. Among the coexisting phases the Al-content of the enstatites increases strongly, with rising temperatures and pressures, up to values approaching that of pyrope composition, whereas the Al-content of the sapphirine solid solution appears to increase only slightly. Concomitantly, the sillimanites, most probably of invariant composition, exhibit growing Al/Si-disorder. These compositional and structural variations, in addition to the changing stoichiometry of the reaction equation, cause the progressively decreasing positive dP/dT slope of the equilibrium curve. — The assemblage sapphirine + quartz found in natural granulites is indicative of conditions of water pressure much lower than total pressure.     

The stability of annite+quartz: reversed experimental data for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite +2 H2O

Reversals for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite+2 H₂O have been experimentally determined in cold-seal pressure vessels at pressures of 2, 3, 4 and 5?kbar, limiting annite +quartz stability towards higher temperatures. The equilibrium passes through the temperature intervals 500–540°?C (2?kbar), 550–570°?C (3?kbar), 570–590°?C (4?kbar) and 590–610°?C (5?kbar). Starting materials for most experiments were mixtures of synthetic annite +fayalite+sanidine+quartz and in some runs annite+quartz alone. Microprobe analyses of the reacted mixtures showed that the annites deviate slightly from their ideal Si/Al ratio (Si per formula unit ranges between 2.85 and 2.92, Al^VI between 0.06 and 0.15). As determined by Mössbauer spectroscopy, the Fe³⁺ content of annite in the assemblage annite+fayalite +sanidine+quartz is around 5–7%. The experimental data were used to extract the thermodynamic standard state enthalpy and entropy of annite as follows: H ⁰ _f,?Ann =?5125.896±8.319 [kJ/mol] and S ⁰ _Ann=432.62±8.89 [J/mol/K] (consistent with the Holland and Powell 1990 data set), and H ⁰ _f,Ann =?5130.971±7.939 [kJ/mol] and S ⁰ _Ann=424.02±8.39 [J/mol/K] (consistent with the TWEEQ data base, Berman 1991). The preceeding values are close to the standard state properties derived from hydrogen sensor data of the redox reaction annite=sanidine+magnetite+H ₂ (Dachs 1994). The experimental half-reversal of Eugster and Wones (1962) on the annite +quartz breakdown reaction could not be reproduced experimentally (formation of annite from sanidine+fayalite+quartz at 540°?C/1.035?kbar/magnetite-iron buffer) and probable reasons for this discrepancy remain unclear. The extracted thermodynamic standard state properties of annite were used to calculate annite and annite+quartz stabilities for pressures between 2 and 5?kbar.     

Stability of manganocordierite and related phase equilibria in part of the system MnO-Al2O3-SiO2-H2O

The pressure temperature stability of the phase Mn-cordierite hitherto not recorded as a mineral has been determined at temperatures ranging from 400° C up to the melting mainly using standard hydrothermal techniques at the oxygen fugacities provided by the buffering power of the bomb walls. Manganocordierite is a pronounced low-pressure phase with a maximum pressure stability of about 1 kb near 400° C and decreasing pressure limits at higher temperatures. Throughout the temperature range investigated the stable high-pressure breakdown assemblage of Mn-cordierite is spessartine, an Al-silicate, and a SiO₂-polymorph. Due to the variable water contents of Mn-cordierite and spessartine there is a pronounced curvature in the negative dP/dT-slope of the requisite upper pressure breakdown curve of Mn-cordierite. Only theoretical deductions were possible concerning the stable hydrous low-temperature breakdown assemblage of Mn-cordierite below about 400° C.The manganocordierites synthesized are orthorhombic low-cordierites with distortion indices increasing with temperature, water pressure, and duration of heating. Their mean refractive indices increase with rising contents of absorbed water in the structural channels. Based on experiments with natural material the upper temperature stability limit of the mineral carpholite must lie at temperatures below about 400° C for water pressures up to 2.5 kb.The absence of Mn-cordierite from natural rocks studied thus far cannot be explained on chemical grounds, but must be due to its narrow pressure temperature stability range. The phase may yet be discovered as a mineral in manganiferous metasediments formed by lowpressure contact metamorphism.     

The stability and phase relations of iron chlorite below 8.5 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Iron chlorites with compositions intermediate between the two end-members daphnite (Fe₅Al₂Si₃O₁₀(OH)₈) and pseudothuringite (Fe₄Al₄Si₂O₁₀(OH)₈) were synthesized from mixtures of reagent chemicals. The polymorph with a 7 Å basal spacing initially crystallized from these mixtures at 300 °C and 2 kb after two weeks. Conversion to a 14 Å chlorite required a further 6 weeks at 550 °C. Shorter conversion times were required at higher water pressures. The products contained up to 20% impurities.The maximum equilibrium decomposition temperature for iron chlorite, approximately 550 °C at 2kb, is at an between assemblages (1) and (2) listed below. Synthetic iron chlorite will break down by various reactions with variable P, T, and fugacity of oxygen. For the composition FeAlSi = 523, the sequence of high temperature breakdown products with increasing traversing the magnetite field for P _total = =2kb is: (1) corierite+ fayalite+hercynite; (2) cordierite+fay alite+magnetite; (3) cordierite+magnetite+quartz; (4) magnetite+mullite+quartz. Almandine should replace cordierite in assemblages (1) and (2) but it did not nucleate. The significance of the relationship between iron cordierite and almandine in this system is discussed.At water pressures from 4 to 8.5 kb and at the nickel-bunsite buffer, iron chlorite+quartz break down to iron gedrite+magnetite with temperature 550 to 640 °C along the curve. At temperatures 50 °C greater and along a parallel curve, almandine replaces iron gedrite. For on this buffer curve, almandine is unstable below approximately 4 kb for temperatures to approximately 750 °C.     

Synthesis and stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10, and Fe3+⇋Al3+ substitutions at 15–28 kb

Deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀, thus far known from ten localities in glaucophane schist terranes, was synthesized at water pressures of 20–25 kb and temperatures of 550–600 °C under the of the Ni/NiO buffer. The X-ray powder diagram, lattice constants and infrared spectrum of the synthetic phase are closely similar to those of the natural mineral. A solid solution series extends from this ferri-deerite end member to some 20 mole % of a hypothetical alumino-deerite, Fe ₁₂ ²⁺ Al ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. The upper temperature breakdown of ferri-deerite to the assemblage ferrosilite +magnetite+quartz+water occurs at about 490 °C at 15 kb, and 610 °C at 25 kb fluid pressure for the of the Ni/NiO buffer. Extrapolation of these data to lower water pressures indicates that deerite can be a stable mineral only in very low-temperature, high-pressure environments.     

The low temperature field of liquid immiscibility in the system K2O-Al2O3-FeO-SiO2 with special reference to the join fayalite-leucite-silica

The extent of the low temperature field of liquid immiscibility in the system K₂O-FeO-Al₂O₃-SiO₂ in the vicinity of the plane fayalite-leucite-silica has been experimentally determined. The combination of direct oxygen buffering with the use of a zirconia probe to monitor oxygen activity has allowed minimisation of K₂O-loss in the experiments while oxygen activity appropriate to the iron-wüstite buffer has been maintained. The four-phase assemblage, fayalite+tridymite+FeO-rich liquid+SiO₂-rich liquid, isobaric univariant in the quaternary system, occurs over a very small temperature range at about 1,163° C on the iron-wüstite buffer. Both liquids appear to be in a coprecipitation relationship with tridymite and fayalite although the relationships between the two liquids are more complicated. The distribution of elements between the two coexisting liquids shows an interesting concordance when plotted in a new way. The results make sense in terms of current knowledge about silicate liquid structure, including the (familiar) observation that K/Al in the SiO₂-rich liquid is always greater than in the coexisting FeO-rich liquid.     

The solubility of alumina in enstatite and the phase equilibria in the join MgSiO3-MgAl2SiO6 at 10–25 kbar

The solubility of alumina in enstatite was determined in the range of 1100–1500° C and 10–25 kbar. The alumina content in enstatite coexisting with sapphirine and quartz increases with increasing temperature and pressure, while that in enstatite coexisting with sapphirine and sillimanite or with pyrope decreases with increasing pressure and decreasing temperature. Two univariant lines, pyrope = enstatite_ss + sillimanite + sapphirine_ss and enstatite_ss + sillimanite =sapphirine_ss + quartz were confirmed. The invariant point involving these phases is metastable. The alumina content of orthopyroxene can not be used either as a pressure indicator or as a temperature indicator without taking the mineral assemblage into account.     

Zur Stabilität von Margarit im System CaO-Al2O3-SiO2-H2O

An increasing number of occurrences of margarite have been reported in the last years. However, previous experimental investigations in the system CaO-Al₂O₃-SiO₂-H₂O are limited to the synthesis of margarite and to the upper stability limit according to the reaction (1) 1 margarite?1 anorthite +1 corundum +1 H₂O (Chatterjee, 1971; Velde, 1971). Since margarite often occurs together with quartz, the upper stability limit of margarite in the presence of quartz is of special interest. Therefore, the reactions (5) 1 margarite +1 quartz ?1anorthite +1 kyanite/andalusite +1 H₂O and (6) 4 margarite+3 quartz ? 2 zoisite+5 kyanite+3 H₂O were investigated experimentally using mixtures of natural margarite (from Chester, Mass., USA), quartz, kyanite, andalusite, zoisite, and synthetic anorthite. The indicated equilibrium temperatures at water pressures equal to total pressure are: 515± 25°C at 4 kb, 545 ±15°C at 5 kb, 590±10°C at 7 kb, and 650±10°C at 9 kb for reaction (5), and 651±11°C at 10 kb, 648 ± 8°C at 12.5kb, and 643±13°C at 15kb for reaction (6), respectively. Besides this, additional brackets for equilibrium temperatures were determined for the above cited reaction (1): 520±10°C at 3 kb, 580±10°C at 5 kb, and 640± 20°C at 7 kb. On the basis of these experimentally determined reactions (1), (5), and (6) and of the reactions (3) 2 zoisite +1 kyanite? 4 anorthite +1 corundum +1 H₂O (7) 2 zoisite +1 kyanite +1 quartz ? 4 anorthite +1 H₂O and (10) 1 pyrophyllite ? 1 andalusite/kyanite+3 quartz+1 H₂O for which experimental or, in the case of reaction (3), calculated data were already available, a pressure-temperature diagram with 3 invariant points and 11 univariant reactions was developed using the method of Schreinemakers. This diagram, summarizing both experimental and phase relation studies, allows conclusions about the conditions under which margarite has been formed in nature. Margarite is limited to low grade metamorphism at water pressures up to approximately 3.5 kb; in the presence of quartz, margarite is even limited to low grade metamorphism at water pressures up to 5.5 kb. Only at water pressures higher than the values stated before margarite, and margarite+quartz, respectively, can occur in medium grade metamorphism (as defined by Winkler, 1970 and 1973). For the combined occurrence of margarite+quartz and staurolite as reported by Harder (1956) and Frey (personal communication, 1973) it may be estimated that water pressure has been greater than approximately 5.5 kb, wheras temperature has been in the range from 550 to 650°C. Furthermore, the present study shows that the assemblage zoisite+kyanite (+ H₂O) is an indicator of both pressure [P _{H 2 O}> approximately 9kb]and temperature [T> approximately 640 to 650° Cat water Pressures up to 15 kb].     

Experimental determination of pargasite stability relations in the presence of orthopyroxene

The stability and partial melting of synthetic pargasite in the presence of enstatitic orthopyroxene (opx), forsterite, diopsidic clinopyroxene (cpx), plagioclase (An₅₀), and water has been studied in the range of 0.4–6.0 kb and 750–1000°C in the system Na₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O with a fixed bulk composition of pargasite+5 opx. The addition of orthopyroxene effectively reduces the stability field of pargasite by approximately 200°C at 1 kb. The invariant point involving pargasite coexisting with water-saturated liquid and anhydrous phase shifts from about 0.85 kb and 1025°C to 2.5±0.5 kb and 925±25°C with the addition of opx. Based on the solidus mineral assemblage and direct chemical analysis of quenched glass, the vapor-saturated liquid has a composition close to that of intermediate plagioclase. A layered silicate, interpreted to be Na-phlogopite, has an upper-thermal stability that nearly equals that of pargasite in the field of partial melting and coexists with liquid, pargasite, cpx, and forsterite at 6 kb, 1000°C. These results support the hypothesis that mantle metasomatism could involve formation of pargasitic amphibole from a silicate melt at depths as shallow as 8–10 km.     

Beginning of melting in the granite system Qz-Or-Ab-An-H2O

The beginning of melting in the system Qz-Or-Ab-An-H₂ O was experimentally reversed in the pressure range kbar using starting materials made up of mixtures of quartz and synthetic feldspars. With increasing pressure the melting temperature decreases from 690° C at 2 kbar to 630° C at 17 kbar in the An-free alkalifeldspar granite system Qz-Or-Ab-H₂O. In the granite system Qz-Or-Ab-An-H₂O the increase of the solidus temperature with increasing An-content is only very small. In comparison to the alkalifeldspar granite system the solidus temperature increases by 3° C (7° C) if albite is replaced by plagioclase An 20 (An 40). The difference between the solidus temperatures of the alkalifeldspar granite system and of quartz — anorthite — sanidine assemblages (system Qz-Or-An-H₂O) is approximately 50° C. With increasing water pressures plagioclase and plagioclase-alkalifeldspar assemblages become unstable and are replaced by zoisite+kyanite+quartz and zoisite+muscovite-paragonite_ss +quartz, respectively. The pressure stability limits of these assemblages are found to lie between 6 and 16 kbar at 600° C. At high water pressures (10–18 kbar) zoisite — muscovite — quartz assemblages are stable up to 700 and 720° C. The solidus curve of this assemblage is 10–20° C above the beginning of melting of sanidine — zoisite — muscovite — quartz mixtures. The amount of water necessary to produce sufficient amounts of melt to change a metamorphic rock into a magmatic looking one is only small. In case of layered migmatites it is shown that 1 % of water (or even less) is sufficient to transform portions of a gneiss into (magmatic looking) leucosomes. High grade metamorphic rocks were probably relatively dry, and anatectic magmas of granitic or granodioritic composition are usually not saturated with water.     

The Stability of Chloritoid Below 10 kb PH2o

The stability of chloritoid, FeAl₂SiO₆H₂O, was investigatedat fluid pressures less than 10 kb. At oxygen fugacities definedby the Ni-NiO buffer, chloritoid reacts to Fe-cordierite andhercynite spinel at 550 and 575 °C at 1 and 2 kb fluid pressure.At pressures between 2.5 and 3.5 kb the assemblage aluminousferro-anthophyllite, staurolite and hercynite spinel appears.The breakdown of chloritoid to this assemblage takes place at625, 650, and 675 °C at 5.5, 7.0, and 8.7 kb, respectively.The aluminous ferro-anthophyllite assemblage is stable onlyover 50 °C, reacting with increasing temperature to almandine,staurolite, and hercynite spinel. Under the QFM buffer, thesame equilibria are displaced to higher temperatures and thealuminous ferro-anthophyllite bearing field is further restrictedwith respect to temperature. The 7 Å chamosite assemblage,previously considered to be the metastable equivalent of chloritoidat low pressures, is shown to be unstable and chloritoid canbe synthesized at pressures as low as 1 kb. An analysis of the equilibria and related experimental datapermits the construction of a schematic P-T grid which outlinesthe stability limits of several important mineral assemblagesin this system. Although the experimental and natural systemsare not strictly analogous, there is an excellent degree ofcorrespondence between the defined upper limit of chloritoidstability and previous estimates of the facies boundaries itserves to define.     

The upper thermal stability of clinochlore,Mg5Al[AlSi3O10](OH)8, at 10–35 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Clinochlore, which is, within the limits of error, the thermally most stable member of the Mg-chlorites, breaks down at = P _tot to the assemblage enstatite+forsterite+spinel+H₂O along a univariant curve located at 11 kb, 838 ° C; 15kb, 862 ° C; and 18 kb, 880 ° C (±1 kb ±10 ° C). At water pressures above that of an invariant point at 20.3 kb and 894 ° C involving the phases clinochlore, enstatite, forsterite, spinel, pyrope, and hydrous vapor, clinochlore disintegrates to pyrope+forsterite+spinel+H₂O. The resulting univariant curve has a steep, negative dP/dT slope of –930 bar/ °C at least up to 35 kb.Thus, given the proper chemical environment, Mg-chlorites have the potential of appearing as stable phases within the earth's upper mantle to maximum depths between about 60 and 100 km depending on the prevailing undisturbed geotherm, and to still greater depths in subduction zones. However, unequivocal criteria for mantle derived Mg-chlorites are difficult to find in ultrabasic rocks.     

Stability of the assemblage orthopyroxene-sillimanite-quartz in the system MgO-FeO-Fe2O3-Al2O3-SiO2-H2O

The stability of coexisting orthopyroxene, sillimanite and quartz and the composition of orthopyroxene in this assemblage has been determined in the system MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-H₂O as a function of pressure, mainly at 1,000° C, and at oxygen fugacities defined mostly by the hematite-magnetite buffer. The upper stability of the assemblage is terminated at 17 kbars, 1,000° C, by the reaction opx+Al-silicate gar+qz, proceeding toward lower pressures with increasing Fe/(Fe+Mg) ratio in the system. The lower stability is controlled by the reaction opx+sill+qz cord, which occurs at 11 kbars in the iron-free system but is lowered to 9 kbars with increasing Fe/(Fe+Mg). Spinel solid solutions are stabilized, besides quartz, up to 14 kbars in favour of garnet in the iron-rich part of the system (Fe/(Fe+Mg)0.30). Ferric-ferrous ratios in orthopyroxene are increasing with increasing ferro-magnesian ratio. At least part of the generally observed increase in Al content with Fe²⁺ in orthopyroxene is not due to an increased solubility of the MgAlAlSiO₆ component but rather of a MgFe³⁺AlSiO₆ component. The data permit an estimate of oxygen fugacity from the composition of orthopyroxene in coexistence with sillimanite and quartz.